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OLEOCHEMICALS, TRENDS AND OPPORTUNITIES
PROF. DR. L.H. STAALandiR. J.W.J. GIELEN Unichema
Gouda, The Netherlands
Natural oils and fats, derived from vegetable and animal sources, are attractive raw materials for a wide variety of so-called oleochemicals. These raw materials are from natural origin with proper management infinitely renewable, non-toxic to our eco-system and fully biodegradable. Furthermore, these raw materials are part of the natural C02 cycle and hence do not contribute to the global heating.
The base oleochemicals, glycerine and fatty acids are obtained by hydrolysis of oils and fats. In particular fatty acids are versatile chemicals which might undergo many chemical conversions of the carboxylic group or the olefinic bonds. The vast range of derivatives find outlets in a wide field of end-uses:
surfactants, soaps, cosmetics and toiletries, polymer building blocks, polymer processing aids, paints and coating, detergents, solvents and cleansers, synthetic lubricants, metal working fluids, hydraulic fluids, emulsifiers, food additives, etc.
Technolo~al Trends. Oleochemicals, being derived from natural raw materials are perfectly suited for biotechnological processes such as: enzymatic splitting, enzymatic esterification and microbial conversion processes. Furthermore, manY. new raw materials and derivatives can be isolated from new or genetically modified oil seed crops, from micro-organisms or algaes.
These new technologies will lead to a better utilisation of feedstocks, reduction of undesirable wasteful products, lower energy consumption and improved quality of endproducts. Moreover, new products can be produced which sofar remain unattainable.
Also progress is being made in conventional catalytic processing and there is a continuous search for cleaner, more selective and more cost effective technology. Recent examples are the synthesis of fatty alcohols from fatty acids at low pressure as alternative for the current high pressure process (300 atm) and the metathesis of oleic acid to c,,dicarboxylic acids. The latter is an interesting new building block for condensation polymers.
705
M.P. C. Weijnen and A. A. H. Drinkenburg (eds.), Precision Process Technology, 105. © 1993 Kluwer Academic Publishers.
PROCESS INTEGRATION OF PRODUCTION AND PRODUCT RETRIEVAL
M.L. Jansen\ J.P.F. de Bruijn\ AJ.J. Straathor, K.Ch.AM. Luyben\ W.J.J. van den Tweel2
1 Delft University of Technology, Department of Biochemical Engineering, Julianalaan 67, 2628 BC Delft, The Netherlands
2 DSM Research, Section CP-BOC, P.O. Box 18, 6160 MD Geleen, The Netherlands
ABSTRACT
Introduction Many (bio )chemical reactions are reversible or are subject to product inhibition or degradation. In these cases process integration of the reaction with a first downstream processing step can enhance the reaction rate and product yield. Additional advantages are that integrated processes are more compact, decrease the contact of reactants, intermediates and products with the environment, and simplify further downstream processing of the product.
Model system As a model system the production of the amino acid L-methionine from N-acetylDL-methionine by enantioselective deacylation with aminoacylase is studied. This reaction is reversible and is inhibited by the produced amino acid and acetic acid1•
A multi-component separation technique is required to separate both products and the unconverted D-enantiomer. Because of the ionic character of the species involved, ion-exchange chromatography is applied. Process integration is accomplished by immobilisation of the enzyme on the ion-exchange resin and by applying the
1m Substrate l&i&.! Product 1 ~ Product 2
Conversion ~
The principle of a pulse-wise operated chromatographic reactor.
combined ion-exchanger/biocatalyst in a packed bed reactor. Racemic substrate is introduced pulse-wise into the column and the L-enantiomer is gradually converted
707
M. P. C. Weijnen and A. A. H. Drinkenburg (eds.), Precision Process Technology, 707-708. © 1993 Kluwer Academic Publishers.
708
on its way through the reactor. Due to the chromatographic action the D-enantiomer is separated from the products. The products are isolated and the unconverted enantiomer is withdrawn, racemised and reused. This process will be carried out continuously in a continuous annular chromatograph2, operated as a chromatographic reactor.
Results Several types of ion-exchange resin have been tested. It was found that with DEAESephadex A25, which is reported to give the highest enzyme activity on immobilisation3, the desired separatiOn can be achieved. This makes it possible to carry out the reaction and separation with the same ion-exchanger/biocatalyst in a single reactor. Process integration of amino acid production and downstream processing therefore seems to be a promising new development. The separation process will be optimised by measuring adsorption isotherms and incorporating them in a computer model for process simulation. Complications may still arise due to the occurrence of intraparticle pH and charge gradients as a consequence of diffusion limitation4•
References 1. C. Wandrey, and E. Flaschel, (1979), "Process development and economic
aspects in enzyme engineering. Acylase L-methionine system", Adv. Biochem. En~ .• 12, 147-218.
2. J.P. J:?eCarli, II, G. Carta and C.H. By~rs, (1990), AI.Ch.E. J., 36, 1220-1228. 3. I. Chtbata, T. Tosa, T. Sato, T. Mon and Y. Matsuo, (1972), Proc. IV IFS:
Ferment. Technol. Today, 383-389. 4. M.L Jansen, AJ.J. Straathof, and K.Ch.AM. Luyben, (1992), "Process inte
gration of amino acid production and separation using chromatographic reactors", Proc. 4th Neth. Biotechnol. Congr., AA Balkema, Rotterdam. C11.
SUBJECT INDEX
absorption 395,407 absorption heat pump 119 absorption in metal hydride slurries, countercur-
rent hydrogen 291 absorption, purification of gas by 384 accessibility of plant data 565 accuracy of data 625 acidic clays 135 activated carbon 225, 226,257, 315, 348, 384,
414 cyanide/silver impregnated activated carb-
on 313 fibers 322, 397 preparation of silver impregnation 307 removal of cyanide with silver impreg-
nated 305 silver impregnated 305, 311
active charcoal 400 active ingredients, preparation of inhomogeneous
distributions 152 active sites, types of 439 activity 602 activity distributions 149 activity of RBE 268 acylation of alky !aromatics 161 acylation of heterocyclic aromatic com-
pounds 161 acylation of phenol and anisole 161 additives 616 adsorbent 341, 351, 384
fouling of 356 regeneration, bleaching earth plant 273 productivity 487
adsorbents, coated 399 permeable 333 regenerable 267
adsorbers, strategy for design 328 adsorption 14,407,508
and desorption phenomena 439 and reaction, coupling 328 affinity 231 , 232 bioproduct in a moving bed 248 co 480 CO at the catalyst surface 480 column 257 columns, continuous 17 Concentration Swing (CSA) 16, 345, 346,401 Concentration Thermal Swing (CTSA) 346,
709
350 constant 485 countercurrent hydrogen in metal hydride
slurries 291 desorption kinetics 332 effects of molecular structure on irreversibility
of 238 equilibria 232 from the liquid phase 225 gas phase 333 in a batch system, mechanisms of 257 in zeolites, gas-phase 238 irreversible 264, 265 kinetics 14 lipase 283 liquid phase 225, 345 membrane 396 micropore 434 monolayer 232 nonlinear 338 of chlorophyll on RBE 269 of hydrophobic secondary metabolites 355 processes and equipment 227 purification of gas by 384 selective 345 single-component 262 two-component 264
adsorption isotherm, equilibrium 327 adsorption systems, mass transfer in liquid 348 adsorptive bioconversion, configurations for 358 adsorptive bioreaction 353 adsorptivereaction 354,371 adsorptivereactions,enzymatic 357 adsorptive reactor, carbon mask 338, 339 adsorptive reactors 15, 327, 338 advanced process control 564, 565, 566 affinitY adsorbents, restricted diffusion of
biomolecules in 237 affinity media 226, 227 air drying 315, 483 air separation 315 air pollution 407 alarm filtering 628 alarm filtering system 623 alarm network 623 alarm presentation 565 alarms 616 alcohols, dehydration of 389
710
alcohol oxidation 162 alginate 78 alkenes, epoxidation of 163 alkyl lactates solvents 81 alkylation,
aromatic hydrocarbons 159 of aromatics 160 of benzene 160 of heteroarenes on zeolites 160 reactions 160
alumina, active 400 aluminas 384 aluminium, production of 519 amine oxidation 162 amino acid production and downstream process-
ing, integration of 708 ammonia compression cycle 98 ammonia production rates, cycle averaged 440 ammonia synthesis 440 ammoxidation 19, 161 analysis, air 524
animal tissues 524 bottom ash 524 bovine milk 524 combustion products 524 fly ash 524 hazardous waste 524 landfill 524 leachate 524 mass spectrometric 508, 511 methods, optical 512 of aqueous solutions with complex composi
tion 512 ofbiopolymers 511 of dioxins, dibenzofurans and PCBs from
incinerators 517 of PCDDs and PCDFs quality control 527 of polychlorobiphenyls 527 of styrene emissions 557 of volatile organic compounds in air and stack
gases 555 particulates 524 sediments 524 sludges 524 soils 524 stack effluents 524 time delay handling 604 wastes 524 water 524
anergy 91 chemical exergy, degradation to 99
anilines 160 annular chromatography, continuous 225,229,
708 argentocyanide complex 305 aromatic hydrocarbons, nitration of 160 aromatic hydroxylation 161 aromatic substitutions, electrophilic and
nucleophilic 159, 169 artificial intelligence 22 artificial intelligence techniques 621 asepsis 356 aseptic barrier 504 aseptic operation 358 assessment of prevention options 677 atom selectivity 126 atom utilization 126, 138 atom utilization in the manufacture of ethylene
oxide 127 attrition resistance 140, 176 attrition-resistant VPO catalyst 175, 176, 177 autoclave reactors 577 automatic analysis, air-segmented 505 automotive catalyst, light-off behaviour of 465
design of 150 automotive emission control, catalytic 463 automotive exhaust catalysts,
dynamic response of 533 kinetic behaviour of 533 kinetics of 534 IICQ labelling of 540
autothermal operation 454 autothermal reactors 453 azeotropes 381 azeotropic distillation 351, 389 azeotropic distillation, vapour permeation
combined with 390
base chemicals 32, 34, 35, 384 batch control 563
models for 611 system 620
batch history 614 batch management 614 batch, multicomponent 257 batch process control requirements 611 batch processes 17 batch reactors 17, 18 batch reports 618 batch sequencing 18 batch system, mechanisms of adsorption in a 257 batch wise conversion of penicillin G 499
batchwise conversions with heterogeneous biocatalysts, numerical model 499
batchwise fermentations 357 bead string reactor 207, 210 Beckmann rearrangement of cyclohexanone
oxime 162, 163 Beckmann rearrangement of oxime 164 benzene, hydrogenation of 221
kinetics of 220 vapor phase nitration over Y -zeolites 160
binary systems 654 bio-active chemicals 75 biocatalysis 419 biocatalyst, efficiency of 493
immobilized 493, 495 immobilized particle 497 design of 493, 496 enzymatic 493 regulating local pH in immobilized 499
biochemical compounds, separation 297 bioconversion 20 biodegradability of diacardoxy-polysac
charides 86 biodegradable 705
lubricants 4}7 plastics 417, 418 polymer 75, 81 printing inks 418
biodegradable polymers, starch-based 87 biodegradation 707 biodegradation of renewable-derived com
pounds 86 biofilters 671 biofilters, styrene-degrading fungi in 671, 672,
679 biofiltration 407 biological degradation 671 biological state of the cells 504 biomass 25, 48
production 77 resources 48 detergents from fossils and 34
biopolymers, analysis of 511 bioproducts, in situ removal of unstable 353 bioreactions, pH-sensitive 371 bioreactor, control 503
membrane 417,419 bioreactors 13
adsorptive 353,354,355 high performance 503
bio-recognition 81, 82, 86
bioseparations 231 biosynthesis 503 biosynthesis of tetracycline 503 bleach activators 81 bleaching earth 267 bleaching earth, regenerable 267 bleaching of pulp 519 bleaching process in edible oil refining 267 bottom ash 518
analysis 524 BSR 211, 216, 207, 210
channel structure in 210 buffer addition 368 buffer components 499 buffer facilitated transport 493 builders and co-builders 81 building block, basic 33, 48
chiral 24, 75,80,81,87,417 butane/decane 654 butane oxidation, kinetic models for 183
capillary condensation 233 caprolactam 164, 165
production of 163 carbohydrate derivatives 75, 78 carbohydrate production, primary 76 carbohydrates 24, 75
as chiral building blocks 83 bio-active 81 bio-catalytic conversion of 75 chemo-catalytic conversion of 75
carbon dioxide 651 carbon dioxide/butane 654 carbon dioxide/butane/decane 658 carbon dioxide/butane system 655 carbon dioxide/decane 654 carbon-dioxide emissions 49
phase behaviour of 654
711
carbon molecular sieve, nitrogen production from air on 333
Carnot cycle 105 Carnot efficiency 117 Carnot factor 91 cascade control 562 catalysis 19
application of W -emitters in kinetic· research 548
enzymatic 19 heterogeneous 139,439,481 homogeneous 139 in waste minimization 125
712
of n-butane oxidation to maleic anhydride 175 of n-butane oxidation to MAN over VPO
catalysts 178 catalyst 139,473,498
activity and decay profile, controlling 577 activity, influence of changing reaction
conditions on 465 activity profiles within 148 carrier characterisation parameters 542 chemisorption of zinc sulphate to
ruthenium 220 CO adsorption at the surface 480 deactivation 437,439 deactivation, effect of diffusion on 147 design 140 design assisted by a computerized process
model 148 Du Pont attrition-resistant 177 dynamic behaviour of 473 eggshell-type 149 eggwhite-type 149 eggyolk-type 149 emission control, catalytic 463 enzymatic 19 heterogeneous 139,140,439,463 monolith 19, 139, 154 morphology 139, 141 morphology, design of 139 morphology in connection with reactor
type 140 morphology tailoring to control catalyst
life 147 partial hydrogenation of benzene to
cyclohexene over ruthenium as a 219 particles 139 particles, intraparticle diffusion in 140 reduction 480 research, improvement of selectivity by 35 size 139 stability of the 447 surface, quantitative information from 548 surface, structural changes 465 with improved hydrogen sulfide suppres
sion 468 catalyst bed, mass balance over the 455 catalysts, base metal 473
bifunctional 167 effectiveness of 141 for oxydative metane coupling 51 halogenation with zeolites x, y and Las 160 regenerability 139
tailoring of 154 catalytic carbonylation 127 catalytic conversion of ethylene into EO 35 catalytic cracking of gas oil 438 catalytic engineering 19 catalytic oxidation 127 catalytic reactions 13 catalytic reduction of NOx in a reverse flow
reactor, selective 453 flue gas treatment, NOx removal by selec-
tive 154 Catalytic Reduction of NOx with ammonia 207 catalytic synthesis of products from CO 45 catalytic systems, integrated design of 154 catalyzed esterifications 363 catcracking processes, modified 35 cause-and-effect tree 626 cell concentration 504 cellulose 75, 76, 77 centrifugal separation 641 centrifuge, alternative plate pack for 641
parallel plate (PPC) 643, 649 centrifuge design, new 641 centrifuges 641 change-over transition 563 chaos 571 charcoal, active 400 chemical labelling 535 chemoselectivity 126 chiral building blocks, carbohydrates as 83 chiral building blocks for pharmaceuticals 418 chiral synthesis from carbohydrates 83 chitin 78 chlorinated dioxins 518 chlorinated phenols 518 chlorination 160 chlorination of benzene, gas phase 160 chlorobenzene (into phenol) over Cu-HZSM5, 1·· hydrolysis of 166 chromatograph, rotating annular 361, 363 chromatographic analysis 508, 511 chromatographic bioreaction 353, 371 chromatographic bioreactors 353, 354, 361 chromatographic effects 152 chromatographic enzyme reactors 363 chromatographic reaction 354,371 chromatographic reactor 15, 338, 368, 708
continuous rotating annular 365 numerical solution fixed bed 378 pulsewise fed 362
chromatographic reactors, fixed bed 361
chromatography 14 affinity 508 gas (GC) 508, 525 ge1permeation 231 hydrodynamics of centrifugal partition 295 ion exchange 508, 707 ionpair 508 linear perfusion 332 membrane 341 moving bed 17 perfusion 332 reversed phase 508 simulated moving bed 14 steady-state 396
Claus process 106 cleaner processes 157 cleaner production 675 closed-loop performance data 633 co-builders 87 co-generation 24 co-generation of olefins and power 52 co-impregnation techniques 152 CO, desorption of 480 CO oxidation 480
heat and mass transfer in Cu-Cr-catalyst 476 in a monolithic catalyst, wall temperature
profile 202 kinetic reaction parameters for catalysed 545 kinetics of 197, 4 73 NO influence on 546
CO oxidation on platinum catalysts, periodic 440 C02 recovery from hydrocarbons and natural
gas 386 of hydrogen from refinery gases 386
coal 48 coke formation 437 combined dual or multiple membrane
processes 401 combustion
offossil fuels 115 of methane 99, 104 of plastic waste 65
commodities 12 compost 519 computer implementation 605 concentration gradient 495 concentration polarization 394 Concentration-Thermal Swing Adsorption
(CfSA) 346, 350 concentration of cultivation medium components
with low molecular weight 504
713
condensation 407 condensation polymers, building block for 705
reactor system and catalyst morphology 140 conservation of feedstocks 50 constrained optimization techniques 574 constraint control 566 constraints for operation 371 contaminant removal from fuels 154 contamination 305 contamination, cyanide treatment systems 305 continuous flow air-segmented automatic analyser
(CPA) 505 continuous processes 17 control algorithms 631
non-linear 631 control architecture 636 control criterion parameters 634 control loops, non-interacting 594 control of bio-technological processes 512 control of trace pollutants 581 control recipe 612, 614, 616 control strategies 578, 602
dynamic 580 control strategies for nonlinear processes 570
new fundamental 577 control strategy design 590, 597 control structure 589 control system 614
reliability of 562 controllability analysis 589, 591, 598 controllability, heater 595 controllability indicators 591 controllers, nonlinear 570 conversion 365 conversion and separation, integration of 353 conversion controls 566 conversion to D-(-)-lactic acid 80 conversion to L-(+)-lactic acid 80 cosmetic wax-esters 417 coupled chemical reactions 95 coupled transport phenomena 499 coupling 14,16 coupling hybrid systems 15 CPC column, flow regime in 301 CPC hydrodynamics 299 CPC, concept of 297
scaling up 299 separation capacity 297 separation efficiency 297 separation mechanism 299
crackers, olefin 50
714
cracking, ethane 34 selectivity 145 thermal 50
cracking of ethane, thermal 57, 58 cracking of heavy paraffins to alpha linear
olefins 39 cracking reactor, integrated 60 crystallization 389,396
fractional 420 and extraction, fractional 418 in-line 420 melt 420 unit, membrane reactor combined with a 420
crystallization processes 383 CSA, ethanol-water separation 346 CSA process, energy for 349 CSA, production of motor fuel grade alcohol
(MFGA) 346 CSA, relative distillation energy 346 CTSA, t)nergy costs for 351 Cu-Cr-catalyst 473 Cu-CR-catalyst, types of reactive oxygen 481 Cu-ZnO catalyst 447 cyanide adsorption rate oilto silver impregnated
activated carbon 308 cyanide breakthrough curves 311 cyanide, concentration monitoring 306 cycle performance 486 cycle time 338 cycled operation of fixed bed reactors 437 cyclic adsorption column operations 238 _cyclic column operation 225, 226, 248 cyclic fixed bed operation 228, 229 cyclic process 17,24 cycling 16,437 cycling of the feed composition 439 cycling of the feed concentrations in non isother
l.mal reactors 441 cy'Cii,qg of the flow direction in non isothermal
r;reactors 442 · cyclodextrins 82 cyclodextrins and derivatives 87 cyclohexanone ammoximation 162 cyclohexanone oxime 163 cyclohexene selectivities of ruthenium
catalyst 219, 220 cycloinulins 83 cyclone reactor 21
data'display 626 deacylation, enantioselective 707
de-oiling equipment 641 de-oiling of water 641, 649 deacylation of penicillin G by immobilized
penicillin acylase 493 decomps 576 degree of purification 365 dehydrogenation 41, 48, 390
propane 438 dehydrogenation and hydrogenation, metal
hydride applications 289 dehydrogenation of 1-butene into butadiene 438 dehydrogenation of propane, ethylbenzene and
amylenes 391 dehydrogenation reactor, combination of with
ceramic membrane 391 denox 159 deposition-precipitation 152 design figures 459 design procedure 460, 570 design requirements 456 desorbent rinse 348 detection criterion 625 detection levels 523 detection limits 557 detection, positional coincident 535 detergent 38, 41, 384 detergent formulation, renewable based 86
carbohydrate derivatives in 83 co-builder in 85 detergent intermediates 41,43 alcohols ex natural fats and oils 43 feedstocks production of 42 from fossil and natural raw materials 37 syngas based products 43
detergent molecules, utilization of ethylene for 41 detergen~~ natural based 41
starting materials 160 detergents production 34 dialysis 404 diastereoselectivity 126 dibenzofurans 518 dicarboxy-polysaccharides 85 diesel exhaust gases, catalytic cleaning of 197 diffusion mechanisms of surface 248 diffusion in the liquid phase of a pore 239 diffusion of multicomponent mixtures 14 diffusion rate in sorption fibers 323 diffusivity, effective 201 2,2-dimethylheptane 145 dimorphecolic acid 418 dioxin emissions 520
disc stacked centrifuge (DSC) 641,642,649 dispersions 14 disposal of harmful substances from waste
water 681 distillation 14, 382
adsorptive and extractive 396 azeotropic 351, 389 catalytic 390 columns, multistage 395 combination with membrane processes 396 diabatic 19 energy costs of 382 inefficient 601
Distributed Control Systems (DCS) 562, 611 down-stream processing 419 drinking water, continuous measurement of
trihalomethanes 558 · drying 14 dynamic behaviour of process 617 dynamic modelling 589 dynamic neurons 631,634 dynamic phenomena 571 dynamic response, open loop 594 dynamic simulation 580 dynamically benign processes 570 dynamics of catalyst response 439
early detection 624 economic optimization 561 edible oil refining 267 eftluentpurification 449 electricity generation 105 electrochemistry 20, 384 electrodialysis, bipolar 396 electroflotation, anodes for 681
of waste water 681 electrosorption 230 electrospray (ES) MS 511 electrostatic coupling 493 emergency episodes 570 emergency venting 571 emission management 675 emission reduction at source 675 empty shells 621 enantio-selective operations 17 enantiomer separation 227 enantioselective hydrolysis of racemic esters 363 enantioselectivity 126 energy consumption 382,383,487, 391, 393, 394,
398,601,705 energy consumption in gas permeation 386
energy consumption of oleochemical process-ing 422
energy demand 407 energy dissipation 18, 19 energy efficiency 348 energy management 18 energy saving 115, 383, 391, 675 energy supply, focused 20
informed 18 energy utilization 18 engineering tools, new basic 570 entropy 19,92 entropy production 19, 93, 95, 97, 98, 106 entropy production equipartition 19, 21 environmental monitoring 555 environmental temperature 91 enzymatic processing 418
integration of 417 enzymatic reactions 13, 14 enzymaticsplitting 705 enzyme 363
immobilization of 358,419
715
on ion-exchange resin, immobilisation of 707 enzyme activity 494 enzyme activity half-life 419 enzyme catalyzed conversions 353, 354, 371 enzyme catalyzed processes 354 enzyme kinetics 493 enzymes, immobilized 493 epoxidation 162 epoxides, rearrangement of 162 equilibrium model 327 equilibrium theory of columns, multi-solute 246 equilibrium theory of columns, single solute 244 equipment failures 616 erucic acid 418 esterification, enzymatic 422, 705 ester hydrolysis, enzyme catalyzed 364 estimation techniques 563 estimator outputs 603 ethane 34, 50 ethane cracking, methane coupling with simul-
taneous 59 ethane/propane 57 ethanol production 34 ethene and propene 68 ethene/propene monomer, recovery 68 ethylene 34
copolymers 571 ethanol from 34
ethylene from natural alcohol 34
716
ethylene manufacturing technology 57 ethylene oligomerisation 40, 41 ethylene oxidation on a silver catalyst 441 ethylene oxide 35 evaporation, double effect 382 exergy analysis, examples of 98 ex situ measurement 504, 510 exergetic efficiency 117 exergy 18,91,92,95,96,97
analysis 18, 89, 90, 91, 95, 97, 98, 106 analysis, illustrated for liquefaction of
methane 96 analysis, illustrated for manufacturing of
ice 98 analysis in the process industry 106 balance 54 chemical 99, 105 chemical, degradation to anergy 99 conservation of 50 degradation of 106 destruction 92 destruction of chemical origin 89 loss of chemical origin 105
exergy losses 49, 54, 89, 98 chemical 105, 106 for steady state flow processes 89
exhaust catalysis research 533 exhaust catalysts 159 exhaust catalysts, automotive 533 exhaust gas composition 465 exhaust gas purification, automotive 473 exhaust gas treatment, automotive 154 exothermic reaction 443 expert systems 22, 566, 621, 622 extraction 14
fractional crystallization and 418 liquid-liquid 14, 396 of fatty acids, membrane 419 of olefins using complexing agents 388 supercritical 15
extractive distillation, adsorptive 396
fabric softeners 81 failure analysis 565 fast atom bombardment (FAB) MS 511 Fast Protein Liquid Chromatography (FPLC) 511 fatty acids, derivatives of 418
selective recovery 420 feed composition 437 feedback, automatic 562
repression 355
feedback control of fermentation process 558 feedback controller, neural network 633 feedforward control 562 feedstocks 24, 65
availability and costs of 43 conservation of 50 changes of 563 glycerine from natural 34 oleochemical 417 primary chemical 384 production of detergent intermediates 42
fermentation 13, 353, 354, 391 adsorptive 355,356 monitoring 553, 558 of solid substrates 13 separation integrated 355
fermentation processes 353 adsorbents in 356 feedback control of 558 secondary metabolite producing 371
fiber beds 317 fibers 317,322,341
compact separation equipment using sorption by 315
hollow 402, 419 polymer 324
fiber sorbents, non-porous 322 fiber sorption, countercurrent 323 fibrous sorbents 231,322, 324,403 filters, adsorptive-chemisorptive 396 fine chemical syntheses 157 Fischer-Tropsch catalysts, effectiveness of 141 Fischer-Tropsch synthesis 440 fixed bed 190, 311 fixed bed catalytic reactors, transient operation
of 437 fixed bed reactors 437
catalystshapes,usedin 144 multitubular 178
flash, calculations three phase 662 flashing and stripping 382 flashing combined with reverse osmosis 387 flow injection analysis (FIA) 505, 510 flow reversal 328
cycle operation with 341 half cycle-time 456
flowability 139, 140 flue gas 518 flue gas sample extraction 524 flue gases, deNOxing of low-dust 210 fluid microstructure 652
fluidizability 139 fluidization behaviour 140 fluidized bed 190
pyrolysis of mixed plastics, costs of 73 fluidized bed reactor, attrition resistance of
catalyst particles 177 multi-stage 359, 360 selective countercurrent adsorbent
transport 360 trickle flow 360
fluidized bed reactors 140 fluidized bed reactors, polymerization of olefins
in 577 fluorescence emission 504 fly ash, analysis 524
from municipal solid waste (MSW) incinerators 518
formation of hydrogen sulfide in an oxidation reduction-cycle 467
fossi. 48 fossil feedstock 34, 46 fossil fuels, use of 115 fossil raw material 32 fossil resources 44, 45 fouling, membrane 504 fouling problems 422 Fourier Transform Infrared (FT -IR)
Spectrometers 512, 533 fractal interfaces 20 fractal nature of surfaces, effect of on sorption
equilibrium 237 fractal objects 20 fractional coverages 259 fractional surface occupancy 259 Friedel Crafts 19 Friedel-Crafts acylation of arenes 161 Friedel-Crafts acylations 135 Friedel-Crafts reactions 160 Fries rearrangement 161 fructans 75, 76 fuel cell electrodes 287 fungi 671 furfural extraction 387 fuzzy control 566 fuzzy logic 22, 566
gas cleaning 227 gas-liquid contactor, centrifugal 21 gas separation 426
dual 396 gascracking 48
gasification 35 gasification of fossil materials 45 gasoil 34, 57 gel chromatographic column 362 genetic engineering 20 glucans 76
cyclic 83 glucose 76
717
hybrid process for conversion to mannitol 79 maltose into 362 isomerization of 357
glucose/fructose 80 glycerine production 34 grade transition strategies 579, 580 gradient elution processes 244 gradient theory 651, 653
near-critical behaviour of 655 scaling behaviour of 659
granular beds 317 green drying 14
haloarenes, hydrolysis of 166 haloaromatics, hydrolysis of 166 halogenation 160 halogenation reactions 160 hazardous wastes, destruction of 559 header 611,613 health and safety and environmental
authorities 613 heat and mass integration 590 heat conduction, axial 200 heater design, optimal 589 heater, integrated parallel 595 heat flow integration 18, 89 heat integration 348, 382, 590, 595 heat pumping, industrial 115
industrial applications 116 heat pump, mechanical 117
principles 116 thermal 116, 117
heat pumps 115 heat pumps, chemical 287
compression 116 (environmental benefits), industrial 115
heat pumps for combined generation of heat and refrigeration 122
heat-wave, migration velocity of 455 temperature gradient 455
heterogeneous biocatalysts, numerical model batchwise conversions with 499
heterogeneous catalysis, low pressure drop
718
reactors for 208, 216 heterogeneous catalytic reactions 338 heterogeneous competitive immunoassay 511 HETP 330 high resolution magnetic mass spectrometer
(HRMS) 526 high-resolution techniques 523 high-temperature applications 436 High Performance Liquid Chromatography
(HPLC) 508 HMF-based polymers 87 hollow fiber membranes 400, 553 hollow fiber modules 404 hollow fibers 402,419
mixed 394 polysulphone 401
homogeneous catalysis 139 homogeneous competitive immunoassay 511 homopolymerization, limit cycle oscillations for
vinyl acetate 571 honeycomb rotor 230 Honeycomb Reactor 207, 208 Hopf bifurcation point 577 hot spots 441 Houdry process 437 HRGC 523 hybrid processes 249 hybrid processes, economic and technical
aspects 381 hybrid systems 230, 407,411,417, 418,
economic aspects of 382 hydrocarbon mixtures, multi-component 661 hydrocarbons, drying of 345 hydrocarbons in effluents, total oxidation of 448 hydroconversion, catalyst design for 147
residue 148 hydrocracking 147, 168 hydrodesulphurisation 147, 148
effect of average pore diameter on the performance of catalysts for residue 148
of gas oil, trickle-flow 141 hydrogen absorption 14 hydrogen gas, storage media 287 hydrogen purification 287, 333,483
continuous slurry process for 292 hydrogenation of benzene 221
of benzene and toluene to cyclohexene and methyl-cyclohexenes, partial 219
of benzene to cyclohexene over ruthenium as a catalyst, partial 219
reactor 601, 602
hydroisomerization, alkane 168 hydrolysis 19 hydrophobic membrane, selectivity 283 hyperfiltration, membrane separation 394
cell394 dual 396, 401
lAST 233 ibuprofen, manufacture of 135 ideal (and real) adsorbed solution 233 ideal work rate 95 ignition temperature 441 immobilized enzyme, penicillin G deacylation
by 498 immunoassay, turbidity 510
interferometric 512 impregnation 152 in situ measurement 504 in situ measurement of cell concentration 504 in situ product removal 356 in situ surface coverage 548 incineration of volatile organic compounds 454 incineration of wastes 519 incinerators, PCDDs and PCDFs from 524 industrial chemicals 384 inert diluents 577 influence parameter 652 information management 616 infrared gas analyser 510 inhibitor 580 inhomogeneous fluid, influence parameters of
the 651,658 initiator efficiency 57 4 inorganic salts in chemicals manufacture 127 inorganic waste 125 integral flow reactor 439 integrated processes 598 integration of enzymatic processing 417 interaction parameters 661, 665 interfacial compositions 652 interfacial tension calculations 651 interfacial tensions 651
computations of 651 estimating 658
interlocking system, automatic 561 intermediate product reservoir 356 intermediate products 616 intermediates 384 internal heat exchanger 448 intra particle mass transfer 309 intraparticle concentration gradients 445
intraparticle convective flow 333 intraparticle diffusion/convection models 334 intraparticle diffusion for non-linear multicom-
ponentexchange 247 intraparticle diffusivity 328 intraparticle Peclet number 329 intraparticle pH-profile 494 inulin 76, 77 ion exchange 232
mixed-bed 396 ion exchange resin, immobilized 363
immobilisation of enzyme on 707 ion exchange resins 225,226,315, 384
neutral or 226 ion exchange sorbents 322 iron and steel, production of 519 iron-titanium alloys 288 irreversible thermodynamics 93 isocratic operation 367 isokinetic sampling 523 isomer-specific analyses 523 isomerization 161
alkane 159 glucose 357 glucose-fructose 362 sucrose/palatinose 80
isomerization of carbohydrates, biocatalyst for 80 Isotope Dilution HRGCIHRMS method 526 isotopically labeled standards 523
jet reactor, gas-solid 21 jets, impinging 21 Joule-Thomson expansion 98
Kalman 566 Kalman estimator 601,602, 604 Kalman filter 22 Kalman theory for discrete linear systems 608 kinematic concentration waves in equilibrium
column exchange 245 kinetic parameters 201 knowledge acquisition 624, 628 knowledge base encoding 622 knowledge-based systems 621 knowledge elicitation 622 knowledge translation 622 Knudsen-type diffusion 141
L-lactic acid and derivatives 87 labelling techniques 533 lactic acid production 360
lactose/lactulose 80 Langmuir isotherm 485 large scale dynamic simulators 579 laser desorption (LO) MS 511 Lateral Flow Reactor 207,210 LDPE 576 lean feeds 444 levan 76 life cycle analysis (LCA) 680 limit cycle oscillations 571, 573 lipase, adsorption of 278 lipases, stability for hydrolysis 420 liquid-liquid extraction, double solvent 396 liquid secondary ion (LSI) MS 511 liquid-vapour tension-pressure 655 local equilibrium model (LEM) 483, 485 long term disturbances 459 long-term scheduling 613 loop reactors 21 lost work 92, 93, 98 low density polyethylene (LDPE) 571, 576 LPG 48 luboils, dewaxing of 383 lubricants 418
magnesium and alloys 288 magnesium, production of 519 maintainability of system 629 maleic acid to tetrahydrofuran, hydrogenation
of 177 maleic anhydride 175, 176
719
reaction pathways for the selective oxidation of n-butane over VPO catalysts 179, 188
selectivity 185, 186, 187 man/machine interface 622, 626, 629 manufacture 35 maps in design and operating parameters 572 marketing 613 mass spectrometry (MS) 396, 523, 525 master control loop 590 measurement input errors 605 melt down of polymer 577 membrane absorption, dual 40 l membrane barriers 504 membrane contactors, multiple fluid-phase 401 membrane, elastomeric 382 membrane emulsion 14 membrane extraction, recovery offatty acids 418,
419 membrane, hydrophobic 276, 283 membrane inlet mass spectrometry (MIMS) 553
720
membrane inlets 553 membrane liquid-liquid extraction, multiple 401 membrane modification with block
copolymers 279 membrane, modified hydrophobic 281 membrane, permeation of mixtures over MFI 430 membrane, polymer 554 membrane processes 20, 382, 396
combined dual or multiple 401 membrane reactor 16,341,417,428
all metal high-temperature 428 biocatalytic hydrolysis in a 418 combined with a crystallization unit 420 combination of and fractional crystalliza-
tion 418 hydrophilic 419
membrane separation 287,293,395,401,417 membrane separation of organic mixtures 385 membrane separation, removal of oil 275 membrane separation technology 384 membrane, silicon 508 membrane-sorbent structures, two-sided 399 membrane-sorbent integrated systems 399 membrane systems, hybrid 417 membrane technology 407, 408, 418
teflon 508 application of 422
membrane units, development of high temperature resistant 386
membrane, unmodified hydrophobic 281 membranes and adsorbents, integration of 399 membranes and sorbents, structural integra-
tion 404 membranes, composite 408
dual separation of OfN2 porous 396 emulsion 14 inorganic 400, 426 inorganic microporous 426 liquid 20,231, 388,408 mass transport phenomena in MFI 426 methyl silicone-based polymers 555 micro-filtration 275 multi-gas permeation, MFI 430 perm-selective 14 polymeric 385 tailor-made 417
menadione, manufacture of 134 metabolic control 371 metal hydride applications, chemical industry 289 metal hydride applications, electrodes 289 metal hydride applications, heat storage 289
metal hydride applications, hydrogen compressors and pumps 289
metal hydride applications, hydrogen-powered vehicles, 289
metal hydride applications, purification of hydrogen 289
metal hydride applications, rechargeable batteries 289
metal hydride applications, storage of hydrogen 289
metal hydride-forming compounds 288 metal hydride slurries 290
countercurrent hydrogen absorption in 291 sorption and desorption of hydrogen 287
metal hydride slurry process 287,290,293 metal hydride (slurry) technology 287 metal hydrides, equilibrium pressure of 288
fixation of 290 hydrogen density of 287
metal hydrides in batch-wise fine chemicals production 292
metal reclamation plants 519 methane coupling 24, 50 methane coupling, catalysts for oxydative 51 methane coupling in a fluid bed reactor 58 methane, liquefaction of 98 methanol formation from C02 and CO 447 methanol production from purge gas 443 methane, steam reforming 140 methanol synthesis 15,444,447
simulation 447 methylisobutylketone, transformation of acetone
on a Pd-ZSM5 168 methyl methacrylate 69, 128 methyl methacrylate manufacture 128 methyl/methacrylate, recovery from PMMA 69 Methyl Tertiary Butyl Ether (MTBE) 390 MFI membrane, single gas permeation 429 MFI zeolites 162 micro-filtration membranes 275 microbial conversion 705 microcapillary membrane-sorbent elements 399 microfiltration 408 microfiltration membranes, protein adsorption
at 275 micromixing 574, 576 minimize liquid inventory 590 minimize use of organic solvents 571 minimum condition number 591,600 mixed plastic wastes from household waste 66 mixed plastics 65
pyrolysis of 65 mixed polyolefins 65 mixers, static 21 mixing 14 mixing, chaotic 21
devices 21 rules 665
mixing parameter, binary 658 mixing parameters, estimates of 659 mixtures of plastic waste 65 Model Predictive Control 22 modelling complex phase behaviour 664 modularization 19 molecular dynamics 248 molecular sieve 384, 388, 389 molecular sieves, air separation on zeolitic
(ZMS) 483 molecular sieves, preconcentration by adsorption
with 389 molecular weight distribution 574 monitor function 566 monitoring industrial emissions and
processes 553 monitoring, positional and temporal 534
selected-ion (SIM) 555 selective ion (SIR) 525
monitoring short-batch cultivations 505 monoglycerides, recovery of 420 monolith, ceramic 198, 200 monolithic Honeycomb catalyst 207 monolithic reactor, catalytic oxidation of carbon
monoxide in a 197 reactor optimization 197 scaling up 197
monoliths, non-ceramic 200 mordenite 161 moving bed, magnetically stabilized 229
simulated 225,229,248, 316 moving beds 225, 229 MSW incinerators 518 multi-component reaction-diffusion system 493,
497 multi-component separation technique 707 multi-component transport 425 multibed adiabatic reactor (MBAR) 444 multicomponent film model 243 multicomponent mixture 393 multicomponent surface diffusion 259 multifunctional reactors 21,425 multilayer (adsorption) 233 multiphase chemical reactions 401
multiphase contactor 393 multiphase process 581 multiple bed units, optimization 483 multiple-ion detection (MID) 523 multiple separation stage 394 multiple steady states 571 multi-solute adsorption, surface diffusion
flux 240 multi-stage fluidized bed reactor, selective
countercurrent adsorbent transport in 359
natural resources 48 n-butane 176 n-butane conversion to MAN, reaction net
work 181 n-butane oxidation, fluidized bed 189
to maleic anhydride, kinetics of 178 to maleic anhydride, catalysis of 175
721
to MAN, fluidized bed performance for 191 to MAN over VPO catalysts, catalysis of 178 to MAN, riser reactor performance for 191 transport bed reactors 189
n-hexane 145 naphtha 50, 57 naphtha feedstock 34 natural feedstocks 34, 417 natural gas 35, 48, 50 natural oils and fats 24, 705 natural resources 44, 417 negative-ion chemical ionization (NCI) 523 neural control, model-based 633 neural controller 633, 639 ' validation of 632 neural nets for process control 631 neural network 22, 631, 632 nickel, production of 519 NIR-Fr multicomponent analysis in food
industries 512 nitrogen and oxygen production from air 483 nitrogen separation on carbon molecular
sieves 483 nodulizing technique 151" non-equilibrium column theory 247 non-porous fibers 322 non-uniform activity distributions 149 non-uniform distributions 152 non-uniform distributions of catalytic
material 148 nonionic surfactants 83 NOx reduction 449 nuclear imaging techniques 535
722
object oriented programming 620 off-gas analysis 508, 510 off-gas treatment, industrial 671 off-spec product 586 offretite 161 offshore oil production 641 oil-displacing agent 651 oil droplet size distribution 64 7 oil production 641 oil recovery, enhanced 651, 662 oil seed crops 705
processing of 422 oils of animal or vegetable origin 267 olefins, ethylene oligomerization to 40 olefins/paraffins separation 388 oleochemicals 24, 705
production of specialty 422 on-line analysis by mass spectrometry 553 on-line analysis of emissions 553 on-line assistance monitoring 622 on-line chromatographic monitoring 508 on-line diagnosis of abnormal events 622 on-line monitoring 508, 511, 512, 622 on-line monitoring of concentration 508 on-line monitoring of protein concentration 511 on-line optimisation 631 on-line process analysis 503 on-line process monitoring 503, 601 on-line sampling 504 on-line techniques 510 on-site monitoring systems 555 open loop stability 594 operating cost 572 operating personnel 613, 614 operating points 632 operating strategies 570 operation and control of hybrid processes 381 operation and control of single unit opera-
tions 381 operation mode for fermentations 357 operation regimes of the RFR 457 operator friendliness 602 operator interface 623 optimal state estimation 609 optimization, strategy 489 organic emissions, minimizing 553 organic solvents 581 organic synthesis 157 out-of-specification production 621 oxidation 19, 407
alkane 162
and ammoxidation 161, 169 of ammonia 105 of ethylene to ethylene oxide 140 of so2 to so3 454 reduction cycles 469
oxidative coupling 50 oxidative methane coupling, fluidized bed for 51 oximes, rearrangement of 169 oxygen overpotential 682 oxygen production from air on SA ZSM 484, 333 oxygen separation from air 487
packed adsorbent column 345 packings, convection on large-pore 328 palmoil 267 Parachor method 651, 652, 653 paraffins, dehydrogenation of 39 parallel configuration 593, 594 Parallel Passage Reactor (PPR) 207,210 paramagnetic gas analyser 510 parameter space classification 574 parametric pumping 14, 328,336, 396
multiple 397, 403 triple 397
parametric pumping and cyclic zone operation in fixed bed 229
paraxylene separation 389 particle permeability 328 partition chromatography, centrifugal 295
liquid/liquid 508 pattern-recognition 618, 622 PCBs 518, 527
analysis of dioxins, dibenzofurans from incinerators 517
PCDDs and PCDFs, analysis of quality control 527 analytical procedure for 523 emissions 520 from incinerators 524 sources of 519
peak detection and quantification 526 pectin 78 Peng-Robinson (PR) equation of state 651, 653,
661,662 periodic processes, kinetic modeling of 441 peptides and oils 681 periodic flow reversal 16 permeation behaviour of multi-gas mixtures 435 permeation behaviour, pure gas 434 permeation,gas 385,386 permselective films 400
pertraction 408 pervaporation 14,16,385,389,391,422
dual or multiple 401 pervaporation enhanced enzymatic esterifica
tion 422 pervaporation enhanced enzymatic esterification
for production of. specialty esters 418 pervaporation, two-membrane 396 pesticides 518 pH-gradients 498 pH-optimum 494 phase behaviour, complex 661 phase labelling 535 phase transformation equilibrium processes 395 phenol, hydroxylation of into hydroquinone and
catechol 163 phenols 160 phenols, synthesis of substituted 166 phenoxy herbicides 518 phenylesters, rearrangement of 161 phloroglucinol, manufacture of 134 phospholipid-removal 422 photochemistry 20 photodegradability 87 photosynthesis 76 photosynthesis by algae 76 PID control 562 pinch technology 18, 89, 95, 121 pinch temperature 121 plant economics 601 plant optimization 564 plasma desorption (PD) MS 511 plastic fraction from household waste (municipal
waste) 69 plastic waste 48, 65
combustion• of 65 pyrolysis of 65, 66 recycling 65
plate pack (curved plates) 646 plate pack (flat plates) 646 plate separators, gravity 641 pollution free grade transitions 579 pollution potential 572 pollution prevention 675 pollution prevention through precision process
modeling, design, and operation 569 pollution reduction 570, 571 pollution reduction targets 676 polychlorobiphenyls, analysis of 527 poly-L-lactate 81 polychlorinated dibenzo-para-dioxins
723
(PCDDs) 517,518 polychlorinated dibenzofurans (PCDFs) 517, 518 polyethylene membranes 555 polymer additives 418 polymer coatings 581
air borne 581 polymer formulations, renewable based 86 polymerization of ethylene, free radical 571
high pressure 576 polymerization of olefins, transition metal
catalyzed 571 polymerization of vinyl monomers, free radi
cal 571 polymerization processes, classification scheme
of 585 condensation processes 584
polymers 384 polyolefins, pyrolysis of 72 polypropylene 37 POLYRED 580 polytetramethylene ether glycol 175 polyvinyl acetate and copolymers 571 pore diffusion 141, 239 pore-filling 233 porous texture 139, 141 Positron Emission computerised Tomography
(PET) 536, 538 PPC, design of 647 precious metal 463 precision chemicals 75 precision conversion of base-chemicals 35 precision process technology tools 572 precision technology 32 precision process technology 11, 449 preconcentrating 381 preconcentration by vapour permeation or
countercurrent flow reverse osmosis 389 predictive control, model-based 631 pressure drop across a BSR 216 pressure drop across channel-like structures 211 pressure drop over CPC-column 301 pressure equalizing 484 pressure swing adsorption (PSA) 293, 328, 333,
398,401,483 prevention options 678 primary metabolites 508 process analysis 121 process automation, batch 611 process characteristics, basic 486 process control 22, 563
basic 564
724
challenge to chemical process engineers 561 precision 601
process down 586 process dynamics 371 process flowsheet, dynamic 580 process heat integration 115 process integration 121 process integration of production and product
retrieval 707 process monitoring 558 process optimization objectives 563 process parameter organization 485 processrevamps,focused 570 process revisions 581 process runaway 570 Process Information System (PINS) 605 productdegradation 358 product grade transitions 570 product grade transitions, minimizing pollution
during 572 product inhibition 355, 707 product purity 486 product quality 563 product recovery ratio in CPC 297 product removal, in-line 417 product selectivity 145 product wheel 580 production management 612 production order base 618 production planning 613 production scheduling 613 production-separation of secondary metabolites,
integrated 355 propane 50 propylene 34 propylene oxide 36 protein adsorption 275 protein adsorption, prevention of 276 protein structure analysis 512 proteins 75 PSi\ 293,328,333,398,401,483
application of 483 basic principles of 484 membrane 403 membrane combinations 399 membrane dual separation 399 membrane gas separation 400 multibed 484, 489
PSi\ processes 484 PSi\ processes, equilibrium vs rate controlled 483 PSi\ systems, dual 398
two-adsorbent dual 403 PTMEG, production of 175 Pt/Pd/ i\lumina catalysts 150 PUFP sampling method 522 PUFP sampling train 522 pulsation 359 pulse labelling experiments 539 purchasing function 613 purge, minimum 487 purge optimization 483 purge,optimum 487 purge step 483 p-xylene by disproportionation of toluene,
selective production 145 p-xylene from toluene, selective formation of 146 pyrolysis of plastic waste, costs of fluidized
bed 73 fluidized bed for 65, 66 rotary kiln 66
pyrolysis oil, dehalogenation of 72 pyrolysis oils and gases 65 pyrolysis oils, organic chlorine in 72 pyrolysis products of mixed plastics 70
quality control, double 566 closed-loop 597 planning and 612 product 563
quality controls 566 quick design procedure 453
racemic mixtures, enantioselective enzymatic resolution of 363
radial flow cell 230 Radio Gas Chromatograph (RGC) 538 radionuclide labelling 535 Raman spectroscopic techniques 533 rare earth alloys 288 Ri\ST 233 rate of work 97 ratio control 562 raw material usage 616 raw materials 32, 34, 705 RE-Y 160 reactant selectivity 145 reaction, coupling of adsorption and 328
coupling and separation 24, 341 reaction and diffusion phenomena in catalyst
particles 140 reaction and separation coupling 15 reaction induced pH-change 366
reaction modelling 541 reactionimage 540 reaction-separation system, integrated 401 reactive chromatography 16 reactive distillation 338 reactive separation 14 reactor data estimator, basic principles 602 reactor dynamics 602 reactor types 190 reactors anQ bioreactors 21 reactors, ebulliated-bed 140 reactors, fixed-bed 140 reactors, moving-bed 140 real-time expert systems for process supervi-
sion 621 real-time supervision 624 real-time training simulation 565 recipe and information management function 611 recipe handling model 614 recipe hierarchy 611, 620 recipe improvement, automation in 611 recipe levels 612 recipe management, batch 620 recipe, master 612, 613,614, 617 recipe model 611 recipe transportability 620 recipe type model 611 Recirculation Solid Reactors 19, 21 recovering waste heat 115 recovery from gas streams 291 recovery from polyolefins 68 recovery, monomer 68 recycle costs 586 recycle options, polymer 46 recycling 65 reduction of the catalyst 480 reduction of waste 705 reference environment 91 refinery gases 35 regeneration 345 regeneration of bleaching earth 268 regioselectivity 126 Relative Gain Array (RGA) 591 reliability of the control system 562 removal of cations 681 removal of NOx from the flue gas 207 removal of organic compounds from water 345 removal of toxic organics 315 removal of trace components 226 removal of trace impurities from liquid 345 remove trace impurities from liquid streams 350
renewable 705 renewables 75 renewables as chemical feedstock 78 representative scenario 634 reproducibility 563 research strategies 25 reservoir engineering 661 reservoir fluids 661
model 661 three-component model 662
residual oils, catalyst design for hydroconver-sion 147
residue gasification processes 48 resources, renewable 417 retrograde behaviour, prediction of 662 retrograde condensation 661 reverse osmosis 14, 382,385, 391 Reverse Flow Reactor (RFR) 453 reversed flow operation 442
modeling of 445 reversed flow reactor 21,442,443 reversed flow reactors, industrial applications
of 448 RFR, design of 453, 456 RFR, typical temperature profile 453 riser reactor 190 robustness 20, 602 Rodrigues equation 331 ROI 448 role of the operator 565 runaway 17, 571
725
conditions, detection of the onset of 578 control of dynamic processes subject to 577 detection 623
runaway detection, incipient temperature 623 runaway potential, predictive estimators 578 runaway side reactions 576 ruthenium catalyst, hydrophilicity of the 223
safety requirements 561 salt-free technologies 127 sample purification 525 sampling 517 sampling methods 521 SAPO molecular sieves 165, 168 scale-down 17 scale-up 17, 372 scheduling and planning 564 scheduling, optimal 618 seedoils 417 selective countercurrent adsorbent transport in
726
multi-stage fluidized bed reactor 359 selective oxidation of n-butane to maleic an
hydride 177, 190 selective oxidation processes 161 Selective Catalytic Reduction of NOx in flue
gases 207 selectivity 17, 20, 126,441,602,604
atom 17 controls 566 for ethylene oxide 442 in organic synthesis 126 intrinsic 17 of heterogeneous catalysts, effect of diffusion
on 144 self-adaptive models 23, 23 sensors 22 - intelligent 23 separation 586
bulk 225, 483, 488 dual 394, 396 factors 403 reaction processes, coupling of 338
separation 24, 341 separation and analysis of biopolymers 511 separation capacity, CPC 297 separation efficiency 486, 641 separation objectives 225 separation of gas mixtures 483 separation of oil from protein-containing emul-
sion 276 separation of organics from diluted solutions 391 separation process, combined 381 separation processes 16, 417
hybrid 16 separation systems, dual 16
characteristics of multiple 393 integrated (dual or multiple) 19, 393 multiple 16, 393,404
separation techniques, combined 393 separation technology in oil refinery industry 382 separation technology in petrochemical in-
dustry 384 separations, adsorptive 327
bulk liquid 345 classification of multiple 395
separators 21 sequence control 563 serendipity 689
negative 697 positive 697 pseudo 697
serial configuration 593 sewage sludge 519 shape selectivity 159 Shell Middle Distillate Synthesis (SMDS) 35 Shell Higher Olefin Process (SHOP) 41 shutdown 589 silica gels 384 silver indicator technique 306 simulated-moving-bed adsorber 345 simultaneous multiple separation 393 simultaneous process and system control
design 589 simultaneous vaporation and freezing 396 single component transport 425 single, dual or multiple transverse-flow 402, 404 single gas permeability 429 single-ion detection (SID) 523 single pass fixed bed 228 single-solute adsorption 240 single substrate-dual product system 354 Single Photon Emission Computerised Tomog-
raphy (SPECT) 537 site recipe 612, 613, 617 situation display 626 size exclusion 232 slave loops 590 slurry reactors 140 slurry viscosity 140 S03-synthesis from metallurgical off gas 448 sol-gel techniques 140 solid catalysts, active sites of 439
recycable 132, 135 solid particle technology 14 solute purification 226 solvent dewaxing process 387 solvent extraction 383, 395 solvent-free process 577 solvent recovery 387, 422
energy costs for 422 energy savings in 386
solventless particle processes 581 sonochemistry 20 sorbent and filtration, mixing with 226 sorbent, regeneration of 315 sorbentia 230 sorbent, regeneration of 315 sorbents 226 sorbitol 78
hydrophobic 355 mixed 394 polymer 400
silica-based 315 sorption 315 sorption columns, granular bed 317 sorption-countercurrent processes 315 sorption-cross-flow gas treatment 316 sorption process· 322 sorption, elastomer.fibers 324 sorption fibers 323 sorption-fluidized bed 316 sorption-forced transport of the solid 316 sorption, in fiber beds 326 sorption-moving bed 316 sorption-moving fluidized bed, column
volume 320 sorption-moving fluidized bed, liquid flow
capacity 320 sorption-moving fluidized bed, pressure drop 320 sorption-moving fluidized bed, separation
effectiveness 320 sorption-moving fluidized beds 316, 319, 320 sorption-packed beds 317,318 sorption-packed beds, equipment volume 318 sorption-packed beds, liquid flow capacity 318 sorption-packed beds, pressure drop 318 sorption-packed beds, separation effective-
ness 318 sorption, polymer fibers 322 sorption process, mass transfer in 326 sorption processes 396
countercurrent 322 countercurrent continuous 316 equipment size reduction in continuous 324
sorption-recovery of organic solvents 315 sorption-revolving circular chromatograph 316 sorption separation equipment, continuous 316 sorption-simulated moving bed 316 sorption systems, cycling parameters 397 sorption, transported fiber bed 323 sour water streams 384 soybean 422 soybean oil 267 SPC/SQC 618 specialties 12, 384 specific product removal 420 SpeedUp 589 stability offatty acids, chemical and thermal 418 stability theory, dynamic 570,571 stable operation 458 stability theory 570, 571 starch 75, 76, 77 starch as a raw material 417
start/stop times 616 start-up heater 453 start-up or shut-down procedures 622 startup 443, 589 stationary cycle 443 steamcracker, typical yield pattern in a
European 32 steam stripping 384 steam stripping of waste water 384 stereo-pure agrochemicals and pharmaceuti-
cals 75 stereoselectivity 17, 126 steric hindrance by pre-adsorbed block
copolymers 276 stirred batch tank 227 storage/release-cycle 467 structural effects of microporous solids 237 styrene, emission of 671 styrene-containing waste gases 671 styrene degradation 671 styrene-degrading fungi 672
727
styrene monomer from polystyrene, recovery 68 styrene removal from waste gases 671 substrate inhibition 503 sucrose 75, 76, 77, 80 sugars, clarification of 345 supercritical fluids 14, 238 supervisory control 562 supply process heat 115 surface diffusion 141,239 surface diffusion, mechanisms of 248 surface plasmon resonance immunosensors 512 surfactant, non-ionic 84 surfactant separation 246 surfactants 81, 87 suspension polymerization, continuous 584 Swedish EPA sampling train 521 swing adsorption, two-parameter 396 syngas 48
based chemistry 48 conversion of 45
synthesis gas by partial oxidation of natural gas 444
synthesis of E-caprolactam 164 synthesis of specialties 417 System for Alarm Filtering and Explanation
(SAFE) 628
tangent plane criterion 662 TAP (Temporal Analysis of Products) reactor
system, DuPont 181
728
TAP (Temporal Analysis of Products) reactor 23, 187
TCDD 517 TCDD-contaminated herbicides 518 technical aspects of hybrid systems 382 Teflon, membranes 508, 555 temporary reservoir 356 tendency models 23 tension-mole fraction relationships 655 terpenes 75 2,3, 7 ,8-tetrachlorodibenzo-p-dioxin 517 tetrahydrofuran (THF) 175, 176
Du Pont process for production of 177 thermal cracking of ethane 59 Thermal Swing Adsorption (TSA) 350 thermo diffusion 95 thermo-economic optimum 89 thermo-economic process analysis 89, 98, 106 thermodynamic coupling 93, 95 thermodynamic efficiency of processes 89, 90,
105 three-way automotive emission control
catalysts 463, 473, 537 three-way catalysis, transient phenomena in 463
·transients in 465 surface properties 468
Tillr02 electrodes 682 titanium silicalite (TS-1) 161, 162, 163, 165 toluene, hydrogenation of 221 total fractionation costs 381 Toxic Equivalent Factors (TEFs) 518 trace analysis of organic compounds from aqueous
solutions 557 trace component separation 483, 488 transfer of information 12 transfer, applicability of 481
behavior of a fixed bed chromatographic reactor 365
behaviour of pH-sensitive immobilized enzyme reactions 496
model 493 applicability 481 operation 16, 437 operation of fixed bed catalytic reactors 437 phenomena (in catalytic systems) 19 phenomena in three-way catalysis 463 processes 17 response method 473 response of UPO catalysis 187
transients in three-way catalysis 465 transport bed reactor, for selective oxidation of n-
butane to MAN 178 application of technology to selective oxida-
tion 178 transport rates of (ionic) reactants 493 tri-block copolymers 276 triglycerides 75
hydrolysis of 419 triple effect flashing 382 TSA 401 tubular reactors, non-adiabatic (multi) 140 tuning and testing 605 tuning parameters 634
ultrafiltration 408 (emulsion separation), dual 401 operations 404
undesirable process situations, prediction of 622 unsteady state processing 16 upper operation regime 458 upset conditions 589 useful work 92, 97 utilisation of feedstocks 705 utility costs 383
va<;:ancy solution theory 233 Vander Waals mixing rules 653 vapour equilibrium, liquid-liquid 661 vapour permeation 385, 390, 408 vapour recompression, mechanical 116, 122 variable costs 448 vegetable oils 34, 38, 417
processing of 422 vegetable resources 417 vemolic acid 418 vinyl acetate hompolymerization, limit cycle
oscillations for 571 vinyl monomers 584 visualization and imaging techniques 23 VOC-removal 415
membranes for 409 voidage 211 volatile organic components 407 volatile organic components (VOC's), removal
from air of 407 VP15 168 VPO catalyst in a porous silica shell 176 VPO catalyst in a transport bed reactor 176 VPO catalysts, transient response 187
warning messages 622 waste and disposal 158
combustion of plastic 65 waste incineration, municipal solid (MSW) 520 waste gas treatment 154 waste heat driven heat transformers 122 waste management 675
integrated 125 waste minimization 126, 675
catalysis in 125 catalytic technologies in 138 in manufacture of catechol 132 in manufacture ofhydroquinone 132 in manufacture ofhydroxybenzenes 132 in manufacture of phenol 132 in manufacture of resorcinol 132
waste production in chemicals manufacture 125 waste water 681 water borne polymer coatings 581 water rinse 348 water softening 315 wax cracking 41 wettability 278 wettability changes 275 world fossil fuel reserves 44
X zeolites 165
Y zeolites 165 vapor phase nitration over 160
yield and product purity 361
zeolite 19, 135, 145, 157, 167, 225,232, 315, 351, 351, 400 5A, oxygen production from air on 333 o:-limonene transformed to p-cymene on Pd
boron 168 -based inorganic membrane reactor 436 -based pressure swing adsorption 287 Beta 161 -catalyzed Friedel-Crafts acylation 137 membranes 427 membranes, MFI 425 paper 397 pore structures 159 silicalite; MFI 425
zeolite catalysts, multistep transformations on 167 zeolites, 5A, synthetic 487
as catalysts 158, 159, 160 gas-phase adsorption in 238 in fine chemical synthesis 157, 159 ion-exchange capability of 158 MFI 162
X 165 y 165
729
X, Y and Las catalysts, halogenation with 160 non-catalytic applications 158
zero emission 125 zero-loss 49 zero-loss concept 49, 50 zero-loss processes 49 zero-loss technology 24 ZSM, oxygen production from air on 5A 484, 333 ZSM-5 145, 147, 161, 162, 165, 166 ZSM-5 zeolite 146
Akzo. Met maar liefst 65.000 mensen in 50 Ianden actief op het gebied van chemie, vezels, verven en lakken, zout en de gezondheidszorg. Levert voor tal van produkten belangrijke grondstoffen.
Akzo nv, Velperweg 76, Postbus 9300, 6800 SB Arnhem.
CREATING THE RICHTCHEMISIRY.
Quality Is the key word at Tebodln~ It Is rigorously controlled throughout all phases of a project , using a quality control system developed In-house.
Tebodin offers wide ranging expenise lor solvmg Industrial environmental problems. This Includes the technical dlsctphnes. but also logistics. economic.s, ecology and environmental law.
Our environmental specialists provide prolesstonal advice to mdustry and the government in the lields ol:
• permit applications
• environmental impact assessment
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• prevention
• environmental care
• HAZOP studies
• risk analyses
• working conditions
• environmental-economic studies
Tebodln B.V. Laan van Nieuw Oost·lndii\ 25 P.O. Box 16029 2500. BA The Hague The Netherlands Telephone: +31 70 3 48 09 11 Teletax: +31 70 3 48 06 45
Hengelo Groningen Maastricht Eindhoven Spljken lsse Beverwljk Arnhem
+3174496496 +3150209555 +31432947n +3140652222 +31188051711 +31 251029332 +3185629171 _j
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Electnctty demand Ructuotet wtdely. More '' used
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These ob1echves mean that pr-oduchon nw~l be planned ortd coordtnoled on o nahonol Kale. h '' for ttHJ reoJOn that the regtOnOI generoltng com· pontes wor\. '" close cooper-chon, w•th Sep os thetr coo-donolong body.
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~ h~~.ct:!~' Arn~~S:~~:=ib?:r:n geon~ product ton ol the country'~_.PC?wer slotlont to odueve maaamum overall COli efficiency. The board controls the nottOnOIIron~mlnlon sys:tcm whteh carries power from the generahng until ro d11tnbuhon compo.ntet. throughou t the country It allO ocu as o central fuel pui"chosmg ag~~ ond regulates the •mport and export of electncdy
In odd•t•ont Sep hos o key role m plai'VImg and pol•cy-molung Every two yeors, it drawt up a nohonaJ Electr•c•ty Plan defln•ng tiM meowres needed to ensure tha t generohng ond tronsm•u•on copoc;•ty w1ll be odequot.e to meel future demand The plan ourlmes srrotegte pol1cy for the wl»e· q.~~l lwo docod01
